CN100537493C - Production of olefins - Google Patents

Production of olefins Download PDF

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CN100537493C
CN100537493C CNB2004800306702A CN200480030670A CN100537493C CN 100537493 C CN100537493 C CN 100537493C CN B2004800306702 A CNB2004800306702 A CN B2004800306702A CN 200480030670 A CN200480030670 A CN 200480030670A CN 100537493 C CN100537493 C CN 100537493C
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crystalline silicate
alkene
hydrocarbon feed
propylene
hydrocarbon
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CN1871191A (en
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让-皮埃尔·达思
沃尔特·弗迈伦
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Total Petrochemicals Research Feluy SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Steroid Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for converting a hydrocarbon feedstock to provide an effluent containing light olefins, the process comprising passing a hydrocarbon feedstock comprising a mixture of a first portion, containing one or more olfeins of C4 or greater, and a second portion, containing at least one C1 to C6 aliphatic hetero compound selected from alcohols, ethers, carbonyl compounds and mixtures thereof, through a reactor containing a crystalline silicate catalyst to produce an effluent including propylene, the crystalline silicate being selected from at least one of an MFI-type crystalline silicate having a silicon/aluminium atomic ratio of at least 180 and an MEL-type crystalline silicate having a silicon/aluminium atomic ratio of from 150 to 800 which has been subjected to a steaming step.

Description

The preparation of alkene
The present invention relates to be used for the convert hydrocarbons raw material contains the effluent of light olefin (particularly propylene) with preparation method.
In petrochemical industry, particularly in order to produce polymkeric substance (particularly polyethylene and polypropylene), for light olefin, for example the needs of ethene and propylene are growing.Particularly, propylene becomes more and more value product, and therefore has the needs of the various hydrocarbon feeds of conversion with the preparation propylene.
Idle (stranded) or association Sweet natural gas that quantity increases have day by day been found all over the world.Not only act as a fuel, if but and might be as the carbon source of chemical and liquid transfer the fuel, the price of stablizing these reserve of gas becomes important.A kind of method that reaches this purpose is to be synthetic gas and then synthesizing methanol with conversion of natural gas, and methyl alcohol can be as the main source of other chemical or liquid fuel.
Known for many years lower molecular weight monohydroxy-alcohol (for example methyl alcohol) is converted into light olefin, and effluent contains ethene and propylene.The methane that exists from Sweet natural gas can easily prepare methyl alcohol, and natural gas supply is abundant, and is excess supply in some produce oil zone in the world.Therefore need be from the feedstock production light olefin from Sweet natural gas, for example ethene and propylene.
At least will contain C from the seventies in 20th century with regard to known 1To C 4The feedstock conversion of monohydroxy-alcohol is the alkene that comprises ethene and propylene.For example the US-A-4148835 of Mobil Oil Corporation has disclosed a kind of Catalytic processes, is used under conversion condition, contacts with the catalyzer that comprises the crystalline aluminosilicate zeolite by making alcohol, contains C and transform 1To C 4The charging of monohydroxy-alcohol (particularly methyl alcohol), the crystallite size of this zeolite is at least about 1 micron, the ratio of silica and aluminum oxide be at least about 12 and restricted index roughly in 1 to 12 scope.Particularly, zeolite comprises ZSM 5.Effluent from methanol conversion comprises ethene and propylene.The problem of the method that discloses in US-A-4148835 is that the productivity of propylene of conversion process is not very high, needs to increase productivity of propylene.
The EP-A-0123449 of Mobil Oil Corporation (and US-A-4788377 of the same clan) has disclosed and has been used to use zeolite catalyst with alcohol/ether, and particularly methanol conversion is the technology of alkene.Olefine selective strengthens by using following zeolite, the crystallographic dimension of this zeolite less than 1 micron and decatize to α value be not more than 50, preferred 5 to 35.Yet the alkene mixture of preparation mainly contains ethene, propylene and butylene, and a small amount of amylene component, does not openly have optionally technology of high propylene.
The DE-A-2935863 of Mobil Oil Corporation (and US-A-4849753 of the same clan) discloses the crystalline aluminosilicate zeolitic that has high silica and alumina ration by use, under about 350 to 600 ℃ temperature and about 1 to 100 atmospheric pressure, with the methyl alcohol catalyzed conversion, prepare the method for light olefin.
This area is also known and is used silica-alumina-phosphate catalyst (being called the SAPO catalyzer) that methanol conversion is light olefin.Recognize with the aluminum oxide-silicate zeolite catalyzer that in US-A-4148835 for example, uses and compare that this catalyzer has the more highly selective for light olefin.For example the US-A-4861938 of UOP, US-A-5126308 and EP-A-0558839 disclose use silica-alumina-phosphate catalyst, and particularly SAPO 34 is the method for light olefin, particularly ethene and propylene with methanol conversion.The problem that these methods exist is particularly when being used for fixing reactor (fixed reactor), and catalyzer is for the poor selectivity of propylene, and has produced too much ethene, causes low relatively propylene/ethylene molar ratio.This has reduced and has contained C 2And C 3The purity of propylene in the fractionation cut of hydrocarbon.And, owing to produced propane, C 3Purified propylene in the cut may be low.In addition, the propylene selectivity is tended in time and instability.Therefore, need provide and have than the high propylene of these currently known methodss method for transformation optionally.
EP-A-0882692 discloses preparation and has had the method for the light alkene of 2-3 carbon atom, be included in first reactor, on the catalysts selective of first form, under 280-570 ℃ and 0.1-1 crust, make methyl alcohol and/or dme steam and the reaction mixture reaction that contains water vapor, from first reactor, take out and contain the alkene of 2-4 carbon atom and the product mixtures of 5 hydrocarbon more than the carbon, and cooling.Refrigerative first product mixtures via the separator charging, and is taken out second product mixtures contain ethene and propylene.Obtain the above logistics of 5 carbon, mix with its gasification and with water vapor.The water that uses and the ratio of hydrocarbon are 0.5 to 3:1.The mixture that contains water vapor is fed in second reactor that contains the second form catalysts selective at 380-700 ℃.Take out the third product mixture from second reactor, it contains 50% olefinic component.Cool off this product mixtures, and be fed to separator.Catalyzer in first reactor can be disclosed silicon zeolite catalyst among disclosed SAPO catalyzer or the US-A-4061724 among disclosed zeolite, US-A-4524235 and the EP-A-0142156 among the EP-B-0448000.Catalyzer in second reactor can be five yuan of supersiliceous zeolites (Pentasil)-type zeolite of 10:1 to 200:1 for silicon/al atomic ratio, and the variant of this catalyzer is disclosed in EP-B-0369364, SAPO catalyzer or silicon zeolite catalyst.
Known use crystalline silicate catalyst, for example from the catalyzer of WO-A-99/29802, catalytic pyrolysis contains olefin feedstock.Need improve this method for the adaptability of the raw material that uses with improve the purified propylene of effluent.And, also need to improve the thermal equilibrium of the reactor that is used for Deep Catalytic Cracking process.
Also known use crystalline silicate catalyst for cracking, preparation light olefin, for example ethene.For example, WO-A-98/56877 discloses and has improved the method for light hydrocarbon raw material to the transformation efficiency of light olefin, comprise following step: hydrocarbon feed is contacted with the catalyst for cracking (for example ZSM-5 zeolite) of preparation light olefin, and the unsegregated air-flow of thermo-cracking then is to prepare extra ethene.
Name people such as Bernhard Lucke is called ＂ CMHC:coupled methanol hydrocarboncracking.Formation of lower olefins from methanol and hydrocarbons overmodified zeolites ＂, Microporous and Mesoporous Materials, 29 (1999) 145-157 (Elsevier Science Publishing, New York, USA, 06-99, in 29 (1-2), first piece of document (XP4167556), the C of use and the common charging of methyl alcohol is disclosed 4Alkene (particularly iso-butylene or 45% iso-butylene, 27% n-butene-(1), 15% n-butene-(2) and 13% just-+mixture of different-butane), carry out the coupling methyl alcohol hydrocarbon pyrolysis (table 3).Catalyzer is for having the zeolite of MFI structure (H-ZSM-5), and Si/Al ratio (synthetic back) is about 16-30.Temperature is 873K or 953K.Effluent contains ethene and propylene, and BTX aromatic substances, methane etc.Yet, only several hours production time (time-on-stream).The author notices female H-ZSM-5 zeolite sample because fast coking and dealuminization and rapid deactivation, and has advised number of ways with modified zeolite, to increase anti-inactivation.A kind of in these approach is at 775K decatize catalyzer (＂ D ＂ represents ＂ dealuminzation ＂).
People's such as identical with first piece of document three authors and S.Nowak name is called ＂ Coupledmethanol/hydrocarbon cracking (CMHC)-A new route to lower olefins frommethanol ＂, Chemical Industries (1992), 46,361-80, the use of 16 industrial H-ZSM-5 zeolite the Si/Al ratio is disclosed in second piece of document (XP8025670) similarly is, and some catalyst oxidation are carried out pre-treatment to reset the Al (extra-frameworkAl) of the extra framework that forms by dealuminzation, described dealuminzation is followed acid leach by handling with decatize.
Name the people such as S.Nowak that have same authors basically is called ＂ An improved methodfor producing lower olefins and gasoline by coupled methanol/hydrocarboncracking (CHMC) ＂, Proceedings of 9 ThInternational Congress on Catalysis, (1988), 4, in another piece document of 1735-42 (XP8025672), catalyzer is SiO 2/ Al 2O 3Ratio (synthetic back) is 31 to 55 H-ZSM-5 zeolite.For methyl alcohol/1-butylene or C 4Fraction charging (Fig. 6), the result is identical with above-mentioned document (XP4167556) table 3.
Name the people such as A.Martin that have same authors basically is called ＂ Coupled conversionof methanol and C4 hydrocarbon (CHMC) on iron-containing ZSM-5 typezeolites ＂, Applied Catalysis, 57, (1990) 203-214 (Elsevier Science Publishers B.V., Amsterdam, in another document of Netherlands (XP8025673), used the ZSM-% catalyzer that contains iron and contain iron-aluminium, a comparative catalyst's Si/Al ratio is 22.
DD-A-270296 (author of its contriver and above-mentioned four pieces of documents is basic identical) discloses and has used the Fe-Al-Si zeolite catalyst to prepare the method for light alkene.
The purpose of this invention is to provide olefinic feed is the method for propylene with the high yield conversion based on alkene, and does not consider the source and the composition of olefinic feed.
Another object of the present invention provides the method that transforms the oxygen-containing hydrocarbon raw material, and described method has the high yield of the high yield of light olefin, particularly propylene.
Another object of the present invention provides the method for the manufacturing propylene with high productivity of propylene and purity.
Another object of the present invention provides following method, and it can make the effluent that contains propylene, and described effluent is at least in chemical grade quality scope.
Another object of the present invention provides the method for making propylene, its have in time stable propylene conversion and stable products distribution.
The invention provides the convert hydrocarbons raw material so that the method for the effluent that contains light olefin to be provided, this method comprises that the reactor of hydrocarbon feed stream through containing crystalline silicate catalyst that make the mixture that contains first part and second section comprises the effluent of propylene with preparation, and one or more C are contained in described first part 4Or high-grade alkene more, described second section contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof, crystalline silicate is selected from following at least a: silicon/al atomic ratio is 150 to 800 MEL-type crystalline silicate at least 180 MFI-type crystalline silicate and silicon/al atomic ratio, and it has experienced steaming step.
Preferably, at least a C in second section 1To C 6Aliphatic series heterocompound and the first part of raw material and the weight ratio of the whole hydrocarbon in the second section are 1 to 99%, more preferably 15 to 85%, more preferably 25 to 50%.
Preferably, at least a C in second section 1To C 6The weight ratio of the whole unsaturated hydrocarbons in the first part of aliphatic series heterocompound and raw material is 0.05:1 to 20:1,0.25:1 to 4:1 more preferably, and more preferably 0.5:1 to 2:1 most preferably is 0.75:1 to 1:1.
Preferably, the second section of hydrocarbon feed contains following at least a: methyl alcohol, ethanol, dme, diethyl ether and composition thereof.
More preferably, the second section of hydrocarbon feed contains methyl alcohol.
Preferably, reactor also is supplied with steam.
Preferably, hydrocarbon feed contains the steam of 80wt% at the most.
Preferably, hydrocarbon feed process crystalline silicate under 350 to 650 ℃ reactor inlet temperature.
More preferably, through crystalline silicate, more preferably described temperature is 460 to 580 ℃ to hydrocarbon feed, most preferably is 540 to 560 ℃ under 400 to 600 ℃ reactor inlet temperature.
Preferably, be 0.5 to 30h at LHSV -1, more preferably 1 to 20h -1Condition under, hydrocarbon feed is through crystalline silicate.
Preferably, when when the crystalline silicate, the dividing potential drop of at least a or multiple alkene in the raw material is 10 to 200kPa.
Preferably, when through crystalline silicate, at least a C in the raw material 1To C 6The dividing potential drop of aliphatic series heterocompound is 10 to 400kPa, and more preferably 20 to 380kPa, most preferably is about 100kPa.
Preferably, total absolute pressure is 0.5 to 50 crust, more preferably 5 to 45 crust.
Preferably, crystalline silicate catalyst comprises that silicon/al atomic ratio is 250 to 500 silicate.
Preferably, the first part of hydrocarbon feed comprise below at least a: hydrotreated original C 4Raw material, LCCS, raffinate 2 raw materials, raffinate 1 raw material, from raffinate 2 raw materials of methyl tertiary butyl ether (MTBE) or Ethyl Tertisry Butyl Ether (ETBE) device, raffinate raffinate from the raffinate of olefin metathesis (metathesis) device (especially for the device of producing propylene from ethene and butylene) or from the logistics that contains hydrotreated alkene of FCC apparatus, viscosity breaker or delay coking stove.
In addition or replacedly, the first part of hydrocarbon feed comprises the product of methyl alcohol to alkene (MTO) technology, contains C4+ alkene.
Randomly, (it contains C to the fraction of effluent 4+ alkene) go back through reactor cycles, constitute at least a portion of hydrocarbon feed first part thus.
The present invention also provides the MFI-type crystalline silicate catalyst in the reactor (silicon/al atomic ratio is 250 to 500) that is infused in altogether of second charging to go up purposes in alkene in the catalytic cracking hydrocarbon charging comprises propylene with manufacturing the method for effluent, it is used for making the thermal equilibrium of this reactor more even, and this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
The present invention also provides the MFI-type crystalline silicate catalyst in the reactor (silicon/al atomic ratio is 250 to 500) that is infused in altogether of second charging to go up purposes in alkene in the catalytic cracking hydrocarbon charging comprises propylene with manufacturing the method for effluent, it is used for increasing effluent propylene/ethylene ratio, and this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
The present invention also provides the MFI-type crystalline silicate catalyst in the reactor (silicon/al atomic ratio is 250 to 500) that is infused in altogether of second charging to go up purposes in alkene in the catalytic cracking hydrocarbon charging comprises propylene with manufacturing the method for effluent, and it is used to increase the C from effluent 3Propylene ratio in the cut, this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
In arbitrary such purposes, preferred second charging comprises methyl alcohol, and the hydrocarbon charging contains one or more C 4Or high-grade alkene more, the weight ratio of the whole unsaturated hydrocarbons in methyl alcohol in second charging and the hydrocarbon charging is 0.5:1 to 2:1, reactor inlet temperature is 540 to 560 ℃.
Therefore the present invention can provide a kind of method, and wherein the hydrocarbon stream (product) from refinery and petrochemical factory not only optionally is converted into light olefin, and particularly is converted into propylene.
Hydrocarbon feed can be under the undiluted situation or with for example charging under the situation of nitrogen dilution of steam and/or rare gas element.In one situation of back, the absolute pressure of raw material constitutes the dividing potential drop of hydrocarbon feed in steam and/or the rare gas element.
Below by example forms, be described in greater detail with reference to the attached drawings all respects of embodiments of the present invention, among the figure:
Fig. 1 show embodiment 1 and 2 and Comparative Examples 1 in, in alkene, the productive rate of ethene and propylene and the relation between the production time in the effluent;
Fig. 2 show embodiment 1 and 2 and Comparative Examples 1 in, with alkene+CH 2Meter, the productive rate of ethene and propylene and the relation between the production time in the effluent;
Fig. 3 show embodiment 1 and 2 and Comparative Examples 1 in, propylene/ethylene ratio in the effluent and the relation between the production time;
Fig. 4 show embodiment 1 and 2 and Comparative Examples 1 in, the alkene purity of propylene and ethene and the relation between the production time in the effluent;
Fig. 5 shows the temperature in the reactor and the relation between the position in the Comparative Examples 1; And
Fig. 6 shows the temperature in the reactor and the relation between the position among the embodiment 1.
Method of the present invention comprises the reactor that hydrocarbon feed is flow through contain such crystalline silicate catalyst, the effluent that contains light olefin (particularly propylene) with manufacturing, described hydrocarbon feed comprises the mixture of first and second portion, and one or more C are contained in described first4Or more senior alkene, described second portion contains at least a C1To C6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyls and composition thereof.
The catalytic pyrolysis of alkene is following to carry out, and the olefin cracking in the first that contains alkene in the hydrocarbon stream that namely merges also optionally is cracked into propylene for light olefin more. What contain in the raw material that hydrocarbon fraction can comprise any kind contains the alkene hydrocarbon stream. The containing hydrocarbon fraction and usually can comprise 10 to 100wt% alkene and can not dilute further or be diluted dilution agent and charging that diluent randomly comprises non-olefin(e) of raw material. Particularly, contain hydrocarbon fraction and can be hydrocarbon mixture, described mixture contains straight chain and branching C4To C10, more preferably C4To C6Alkene, randomly with C4To C10Straight chain and branched paraffin and/or aromatic compounds mix. Usually, the boiling point that contains olefin stream is approximately-15 ℃ to about 180 ℃.
In the particularly preferred embodiment of the present invention, the containing hydrocarbon fraction and can comprise C from oil plant and steam cracking device of hydrocarbon feed4Mixture. The large-scale raw material of this steam cracking device cracking comprises ethane, propane, butane, naphtha, diesel oil, fuel oil etc. More specifically, hydrocarbon feed contains hydrocarbon fraction and can comprise C from the fluid catalytic cracking in the crude oil refinery factory (FCC) device4It is gasoline and lighter products more that cut, this device are used for heavy oil transformation. Usually, from this C of FCC apparatus4Cut comprises about 50wt% alkene. Perhaps, hydrocarbon feed contain hydrocarbon fraction can comprise from the crude oil refinery factory for the production of the C of the device of methyl tertiary butyl ether(MTBE) (MTBE)4Cut, described ether is from methyl alcohol and isobutene preparation. Equally, from this C of MTBE device4Cut generally includes about 50wt% alkene. These C4Cut is in the outlet fractionation of each FCC or MTBE device. The hydrocarbon fraction that contains of hydrocarbon feed can further include C from the naphtha steam cracking device of petrochemical factory4Cut is about 15 to 180 ℃ C comprising boiling point5To C9The naphtha of material is produced C 4 fraction etc. by steam cracking. This C 4 fraction generally includes (by weight) 40 to 50%1,3-butadiene, about 25% isobutene, about 15% butylene (form of 1-butylene and/or 2-butylene) and about 10% normal butane and/or iso-butane. The containing hydrocarbon fraction and also can comprise the C that comes (raffinate 1) after the comfortable extraction butadiene or the steam cracking device after butadiene hydrogenation of hydrocarbon feed4Cut comprises hydrotreated C thus4(this area is called the hydrotreated original C of ＂ in logistics4The ＂ logistics), original C4Raw material or from raffinate 2 raw materials of MTBE or ethyl tert-butyl ether (ETBE) (ETBE) device, or from the raffinate of olefin metathesis device.
The containing hydrocarbon fraction and can also replacedly comprise the C that is rich in hydrogenated butadiene of raw material4Cut is usually greater than 50wt% C4As alkene. Replacedly, the containing hydrocarbon fraction and can comprise pure olefin feedstock of hydrocarbon feed, it prepares in petrochemical factory.
Raw material contain that hydrocarbon fraction can also further replacedly comprise slight cracking naphtha (LCN) (perhaps being called slight catalytic pyrolysis petroleum solvent (light catalytic cracked spirit) (LCCS)) or from the C of steam crackers or slight cracking naphtha5Fractionation is out from the effluent of the above-mentioned FCC apparatus of crude oil refinery factory for cut, described slight cracking naphtha. These two kinds of raw materials all contain alkene. The containing hydrocarbon fraction and also can further replacedly comprise the moderate cracking naphtha (medium cracked naphtha) from this FCC apparatus or come in the comfortable crude oil refinery factory visbreaking naphtha for the treatment of the viscosity breaking plant of the residue of vacuum distillation plant of raw material, perhaps coking furnace naphtha. The containing hydrocarbon fraction and can replacedly comprise raffinate 2 raw materials of raw material, contain alkene but have high isoparaffin content.
The containing hydrocarbon fraction and can replacedly include or contain methyl alcohol to the product of alkene (MTO) technique of raw material, this product contains C4+ alkene for example is described in those of US-A-4148835, EP-A-0123449 and DE-A-2935863 and above-mentioned US-A-4849753 of the same clan thereof. The effluent of the inventive method contain C4The fraction of+alkene can circulate back through reactor, is configured for thus at least a portion of the alkene charging of the inventive method.
The containing hydrocarbon fraction and can comprise one or more mixture in the above-mentioned raw materials of raw material.
Use C5Cut contains hydrocarbon fraction or uses C in containing of hydrocarbon feed in the hydrocarbon fraction as hydrocarbon feed5Cut has superiority especially, removes C because under any circumstance need from the gasoline of oil plant manufacturing5Material. This is because of C in the gasoline5Existence increased ozone potential energy (ozone potential), therefore increased the photochemical activity of gained gasoline. Using in the situation that contains hydrocarbon fraction of slight cracking naphtha as raw material, reducing the olefin(e) centent of residue gasoline part, thereby reducing vapour pressure and the photochemical activity of gasoline.
Contain at least a C1To C6The catalyzed conversion of hydrocarbon steam second portion of aliphatic series heterocompound making light olefin, particularly ethene and propylene in effluent, and optionally is propylene, and described aliphatic heterocompound is selected from alcohol, ether, carbonyls and composition thereof.
C 1To C6Aliphatic alcohol can be for monohydric alcohol and straight chain or branching, and can be selected from methyl alcohol, ethanol, propyl alcohol and butanols. Ether can be C2To C4Ether is selected from dimethyl ether, diethyl ether or methyl ethyl ether. Carbonyls can be C2To C4Carbonyls is selected from formaldehyde, Ketene dimethyl or acetic acid. The second portion of raw material most preferably is selected from methyl alcohol, ethanol, dimethyl ether, diethyl ether and composition thereof, particularly preferably methyl alcohol. The method according to this invention, the hydrocarbon feed that contains the first and second parts of merging optionally transform in the presence of MFI-type or MEL-type catalyst, to make propylene in the gained effluent. Selecting catalyst and process conditions are so that this technique has the specific conversion ratio of the propylene in the effluent.
According to a preferred aspect of the present invention, catalyst comprises the crystalline silicate of MFI family, it can be any other silicate of zeolite, silicon zeolite (silicalite) or this family, or the crystalline silicate of MEL family, and it can be any other silicate of zeolite or this family. Trigram title ＂ MFI ＂ and ＂ MEL ＂ represent specific crystalline silicate structure type separately, such as Structure Commission of the International Zeolite Association defined. The example of MFI silicate is ZSM-5 and silicon zeolite. The ZSM-11 that the example of MEL zeolite is known in the art. Other example is Boralite D and silicon zeolite-2, as International zeolite Association (Atlas of Zeolite structure types, 1987, Butterworths) described.
Preferred crystalline silicate has hole or passage and the high silicon/al atomic ratio that is limited by ten oxygen rings.
Crystalline silicate is microporous crystalline inorganic polymer, and it is based on passing through to share oxonium ion XO connected to one another4The tetrahedron skeleton, wherein X can be (for example A1, the B...) of trivalent or tetravalence (for example Ge, Si ...). The crystal structure of crystalline silicate limits by concrete order, and wherein the network connection of tetrahedron element together. The size of crystalline silicate pore perhaps replacedly, is determined by forming the cationic character that exists in the required oxygen atom number in hole and the hole by the number of tetrahedron element. They have the unique combination of lower surface properties: high internal surface area, the even hole with one or more discrete size, ion interchangeability, good heat endurance, the ability of absorption organic compound. Because the hole of these crystalline silicates is similar with the size of actual interested many organic molecules, the turnover of their control reactants and product causes specific selective in the catalytic reaction. Crystalline silicate with MFI structure has the following bidirectional crossed hole system in aperture: along the sinusoidal passage on the straight channel of [010]: 0.53-0.56nm and edge [100]: 0.51-0.55nm. Crystalline silicate with MEL structure has bidirectional crossed straight hole system, and it has the straight channel of the edge that the aperture is 0.53-0.54nm [100].
Crystalline silicate catalyst has structure and chemical property, and uses under special reaction condition, is easy to thus carry out catalyzed conversion to form light olefin, particularly propylene.
Catalyst has high silicon/al atomic ratio, and catalyst has relatively low acidity thus. In this manual, the Si/Al atomic ratio of term ＂ silicon/al atomic ratio ＂ intention expression all material, it can be determined by chemical analysis. Particularly, for crystalline silicate material, described Si/Al ratio is not only applicable to the Si/Al skeleton of crystalline silicate, and is applicable to all material.
Different response paths can occur on catalyst. Intensity and the density in sour site are directly related on hydrogen transfer reaction and the catalyst, and this reaction preferably by using high Si/Al recently to suppress, in order to avoid forming coke in conversion process, increases the stability of catalyst thus. And, find to use high Si/Al atomic ratio to increase the Propylene Selectivity of catalyst, namely reduce the amount of the propane that produces and/or increase the propylene/ethylene ratio. This has increased the purity of gained propylene.
According to an aspect of the present invention, the first type of MFI catalyst has high silicon/al atomic ratio, for example at least about 180, is preferably greater than approximately 200, and more preferably greater than about 250, this catalyst has lower acidity thus. Intensity and the density dependent in hydrogen transfer reaction sour site directly and on the catalyst preferably suppress this reaction, avoiding forming gradually coke, and coke and then will reduce catalyst stability in time. This hydrogen transfer reaction tends to produce saturate for example unsettled diene and cycloolefin and the aromatic compounds of alkane, centre, and these materials can not help the conversion to light olefin. Cycloolefin is the precursor of aromatic compounds and coke shape molecule, and particularly in the presence of solid acid, namely acidic solid catalyst exists lower. The acidity of catalyst can be by contacting with ammonia (it is adsorbed onto on the sour site of catalyst) at catalyst, and then at high temperature ammonia quantitative determination remaining on the catalyst is measured in the differential thermogravimetric analysis of passing through after the ammonium desorption. Preferred silicon/aluminum ratio most preferably is 250 to 500 in 180 to 1000 scope.
When crystalline silicate catalyst has so high silicon/aluminum ratio, can realize the stable conversion of hydrocarbon feed, and have high productivity of propylene. Silicon/al proportion that this of catalyst is high has reduced the acidity of catalyst, thereby has also increased the stability of catalyst.
The MFI catalyst with high silicon/al atomic ratio that is used for catalysis conversion method of the present invention can prepare by removing aluminium from commercially available crystalline silicate. Usually commercially available silicon zeolite silicon/the al atomic ratio example is about 120. Commercially available MFI crystalline silicate can pass through the Steaming modification, and this technique has reduced the tetrahedral aluminium in the crystalline silicate framework, and the aluminium atom is converted into the octahedra aluminium of amorphous alumina form. Although in steaming step, the aluminium atom to be removed with chemical mode from crystalline silicate framework structure, thereby formed alumina particle, these particles cause hole or the passage in the partial blockage skeleton. This has suppressed conversion process of the present invention. Therefore, after steaming step, crystalline silicate is carried out extraction step, wherein amorphous alumina is removed from the hole, and at least part of recovery of micro pore volume. By the leaching step carry out physics is removed the total effect that has produced MFI crystalline silicate dealuminization by forming the water-soluble aluminum compound from the hole with amorphous alumina. With by from the MFI crystalline silicate framework, removing aluminium, then from the hole, remove this mode of the aluminium oxide of formation, the method purpose is to realize basic uniformly dealuminization at institute's perforated surface of catalyst. This has reduced the acidity of catalyst, has reduced thus the generation of the hydrogen transfer reaction in conversion process. Substantially equably occur during the institute that this reduction of acidity limits in crystalline silicate framework ideally is porose. This is that hydrocarbons can enter the depths in hole because in hydrocarbon conversion process. Thus, carry out in whole pore structures of minimizing (this will reduce the stability of MFI catalyst) in skeleton of the reduction of acidity and the hydrogen transfer reaction that therefore causes. Framework silicon/aluminum ratio can be increased at least about 180 by the method, and is preferred about 180 to 1000, and more preferably at least 200, more preferably at least 250, and most preferably 250 to 500.
Two pieces of documents below, the name that is the people such as Bernhard Lucke is called ＂ CMHC:coupled methanol hydrocarbon cracking.Formation of lower olefins from methanol and hydrocarbons over modified zeolites ＂, Microporous and Mesoporous Materials, 29 (1999) 145-157 (Elsevier Science Publishing, New York, USA, 06-99,29 (1-2) (XP4167556) and the people's such as S.Nowak ＂ Coupled methanol/hydrocarbon crack (CMHC)-A new route to lower olefins from methanol ＂, Chemical Industries (1992), 46,361-80, (XP8025670) in, carry out the hydrocarbon pyrolysis of coupling methyl alcohol although disclose the use zeolite catalyst, described catalyst experience ＂ processes (then acid leach) by decatize and carries out dealuminzation, with the extra framework ＂ of the aluminium that reset to form, the Si/Al ratio that these documents do not disclose or hint increases catalyst to limit such as specification of the present invention at least 180. In this manual, as mentioned above, term ＂ silicon/al atomic ratio ＂ refers to the Si/Al atomic ratio of all material, and it can be determined by chemical analysis. Particularly, for crystalline silicate material, the Si/Al ratio of regulation not only is applicable to the Si/Al skeleton of crystalline silicate, and is applicable to all material. In above-mentioned two pieces of prior art documents, disclosed the dealuminization on the meaning of removing framework aluminum, but the Si/Al ratio that does not openly increase all material is at least 180 scope.
Except MFI-type catalyst, it is 150 to 800 MEL-type crystalline silicate that method of the present invention also can be used silicon/al atomic ratio, and it has experienced steaming step. According to a further aspect in the invention, can be by decatize synthetic (as-synthesised) or commercially available crystalline silicate manufacturing for the MEL catalyst of catalytic hydrocarbon method for transformation. Be used for MEL crystalline silicate catalyst major part of the present invention and comprise the ZSM-11 catalyst, it can use diamino-octane as template (templating agent) and sodium metasilicate synthesizes as the silicon source or use Si butyl phosphonium bromide synthetic as the silicon source as template and Ludox. Therefore the ZSM-11 catalyst can be made in the following manner: sodium metasilicate and 1,8 diamino-octane are mixed with aluminum sulfate together, form hydrogel, then make its crystallization form crystalline silicate. Then remove the organic formwork material by calcining. Replacedly, by Si butyl phosphonium bromide and NaOH are prepared the ZSM-11 catalyst with the Ludox reaction of making from colloidal silica together. Equally, carry out crystallization to produce crystalline silicate, then calcined product.
In order to reduce the sodium content of MEL crystalline silicate, use the salt pair crystalline silicate to carry out ion-exchange. Dry this material afterwards. Usually, crystalline silicate and ammonium ion carry out ion-exchange, for example pass through at NH4Cl or NH4NO 3Flood crystalline silicate in the aqueous solution. If the concentration of sodium ion is so high in the crystalline silicate, so that after the crystalline silicate calcining, formed the crystalline sodium disilicate phase that is difficult for removing, then need this ion-exchange step.
Initial MEL crystalline silicate can pass through the Steaming modification, and this technique it is believed that and is not limited to theory, can reduce the tetrahedral aluminium in the crystalline silicate framework, and the aluminium atom is converted into the octahedra aluminium of amorphous alumina form. Although in steaming step, as if the aluminium atom is removed with chemical mode from the MEL crystalline silicate framework structure, form alumina particle, but these particles does not move, therefore and can not cause hole in the skeleton or the Partial Blocking of passage, otherwise will suppress conversion process of the present invention. Have been found that steaming step significantly improves the productivity of propylene of catalytic conversion process, Propylene Selectivity and catalyst stability.
Processing dividing potential drop at high temperature (preferably at 425 to 870 ℃, more preferably 540 to 815 ℃ temperature) and atmospheric pressure and water for the decatize of MEL catalyst is to carry out under 13 to 200kPa the condition. Preferably, carrying out decatize in the atmosphere that comprises 5 to 100% steam processes. Decatize is processed and was preferably carried out more preferably 20 hours to 100 hours 1 to 200 hour. As mentioned above, decatize is processed the amount that is tending towards reducing by forming aluminium oxide tetrahedral aluminium in the crystalline silicate framework.
After steaming step, calcining MEL catalyst for example under 400 to 800 ℃ temperature, was under atmospheric pressure calcined 1 to 10 hour.
After steaming step, the MEL catalyst can contact the complexing agent (complexing agent) for aluminium, and described complexing agent can comprise with the acid of its aqueous solution form or salt that should acid or the mixture of two or more described acid or salt. Complexing agent can comprise amine particularly, for example ethylenediamine tetra-acetic acid (EDTA) or its salt, particularly its sodium salt. After MEL crystalline silicate contact complexing agent, crystalline silicate can carry out the ion-exchange step second time, is used for further reducing the sodium content of crystalline silicate, for example by contact catalyst and ammonium nitrate solution.
Required form, the pill of for example extruding can be mixed and be shaped to MEL or MFI crystalline silicate catalyst with adhesive (preferred inorganic bond). Select adhesive, so that the temperature of using in opposing catalyst manufacturing process and the catalytic conversion process afterwards and other condition. Adhesive is inorganic material, is selected from clay, silica, metal oxide (ZrO for example2) and/or metal, or comprise the gel of the mixture of silica and metal oxide. Adhesive is oxygen-freeization aluminium preferably. Yet, can use the aluminium that is present in the specific compound, for example AlPO4In aluminium because latter's inertia is very large, and be not acid in nature. If the adhesive that is combined with crystalline silicate itself is catalytic activity, then this can change the conversion of catalyst and/or selective. Inert material for adhesive can be used as diluent suitably, and therefore the amount so that control transforms can obtain product economical and in an orderly manner, and does not use the device of other control reaction rate. Provide and have good crushing strength the catalyst of (crush strength) is desirable. This is because in commercial use, prevents that catalyst breakage from being that dusty material is desirable. This clay or oxide adhesive mostly just are used for improving the crushing strength of catalyst. Particularly preferred adhesive comprises silica for catalyst of the present invention.
The relative scale of crystalline silicate material in small, broken bits and the inorganic oxide matrix of adhesive can wide variation. Usually, the binder content of composite catalyst is 5 to 95 % by weight, is more typically 20 to 50 % by weight, based on the weight of composite catalyst. The mixture of crystalline silicate and inorganic oxide adhesive is called the crystalline silicate of preparation.
When mixed catalyst and adhesive, catalyst can be mixed with pill, extrudes to be other shape, or is shaped to spray-dired powder.
Usually, by expressing technique tackiness agent and crystalline silicate catalyst are mixed.In this technology, tackiness agent, for example silica is with the form and the crystalline silicate catalyst material mixing of gel, and the gained mixture is extruded and is desired shape, for example pill.Afterwards, the crystalline silicate of calcining preparation in air or rare gas element is usually 200 to 900 ℃ of calcinings 1 to 48 hour.
Tackiness agent does not preferably contain any aluminum compound, for example aluminum oxide.This is because as mentioned above, and preferred catalyzer has the selected silicon/al proportion of crystalline silicate.If before extracting the aluminium step, carry out adhesion step, in tackiness agent, exist aluminum oxide to cause other excessive aluminum oxide.If aluminiferous tackiness agent and crystalline silicate catalyst are mixed after extracting aluminium, this causes making catalyzer aluminic acid salinization again.In tackiness agent, exist aluminium will often reduce the propylene selectivity of catalyzer, and reduce catalyzer stability in time.
In addition, mixed catalyst and tackiness agent can carry out before or after any steaming step.
Have been found that various preferred catalyzer have high stability.This makes catalytic conversion process to carry out continuously in two parallel " shaking (swing) " reactors, and during one of them reactor work, another reactor carries out catalyst regeneration.The catalyzer several times of also can regenerating.Catalyzer also is flexibly, because it can be used for the cracking plurality of raw materials, and perhaps pure raw material or mixture material, described raw material is from refinery or petrochemical factory and have different compositions.
In catalytic conversion process, select processing condition, so that the highly selective to propylene is provided, distribute to the stable conversion of propylene and the stable product of effluent in time.These purposes are by using low sour density (being high Si/Al atomic ratio) and realizing in conjunction with low pressure, high temperature in and short contacting time in catalyzer uses, all these processing parameters all are correlated with, and whole accumulative effects (overallcumulative effect) (for example higher pressure can be offset or compensation by higher temperature in) are provided.Select processing condition, to be unfavorable for causing forming the hydrogen transfer reactions of paraffinic hydrocarbons, aromatic substance and coke precursors.Therefore process conditions is used high-speed, low pressure and high reaction temperature.
With respect to compound hydrocarbon feed, the scope of liquid hourly space velocity (LHSV) is 0.5 to 30h-1, and preferred 1 to 20h -1, 10h more preferably from about -1Compound hydrocarbon feed is preferably to be enough to that raw material is carried the main entrance pressure charging of passing through reactor.Preferably, the total absolute pressure in the reactor is 0.5 to 50 crust, more preferably 5 to 45 crust.The dividing potential drop of aliphatic series heterocompound (one or more) can be preferably 20 to 380kPa for 10 to 400kPa, and more preferably 50 to 200kPa.Particularly preferred aliphatic heterocompound dividing potential drop is 100kPa.Olefin partial pressures is 10 to 200kPa.Particularly preferred olefin partial pressures is 100kPa (being approximately normal atmosphere).Top hole pressure is generally 1.5 crust.
At least a C in the raw material 1To C 6The aliphatic series heterocompound is 1 to 99% with whole part by weight of hydrocarbon, more preferably 15 to 85%, more preferably 25 to 50%.
At least a C in the raw material 1To C 6The aliphatic series heterocompound is 0.05:1 to 20:1 with whole part by weight of unsaturated hydrocarbons, 0.25:1 to 4:1 more preferably, and more preferably 0.5:1 to 2:1 most preferably is 0.75:1 to 1:1.
Compound hydrocarbon feed can not dilute charging or dilute charging (for example use 0 to 80wt% steam, be generally about 30wt% steam dilution) through steam, and/or charging in rare gas element (for example nitrogen or hydrogen).Use low aliphatic heterocompound dividing potential drop, normal atmosphere for example tends to reduce the incidence of hydrogen transfer reactions in the conversion process, this so that reduced potential that the coke that tends to reduce catalyst stability forms may.Preferably, the temperature in of raw material is 350 to 650 ℃, more preferably 400 to 600 ℃, more preferably 460 to 580 ℃, is typically about 540 ℃ to 560 ℃.
Catalytic conversion process can carry out in fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor.Common fluidized-bed reactor is the FCC type reactor that is used for fluid catalytic cracking in refinery.Common moving-burden bed reactor is a continuous catalytic reforming type reactor.As mentioned above, this technology can be used pair of parallel " to wave " fixed-bed reactor to carry out continuously.
Because catalyzer demonstrates secular high stability, the regeneration frequency of catalyzer is low.Therefore more particularly, catalyzer can have and is higher than the life-span in 1 year.
The lightweight fraction of effluent, i.e. C 2And C 3Cut can contain the alkene (being ethene and propylene) greater than 90%, contains ethene and propylene greater than 90% usually.This cut is enough pure, to constitute the olefin feedstock of chemical grade.Productivity of propylene can be 35 to 45% in this technology, and productivity of propylene is with ＂ alkene+CH 2＂ is a basic calculation, and supposes that each methanol molecules constitutes the ＂ CH for any alkene that exists in the raw material 2The ＂ source.Mixed C 2/ C 3In the fraction, propylene/ethylene weight ratio is generally 3:1 to 9:1, is more typically 4:1 to 7:1.C 3The propylene of cut accounts for whole C usually 3More than the 97wt% of cut (propylene and propane), more generally more than the 98wt%.
The method according to this invention, by while converted olefin logistics and methyl alcohol is light olefin, described light olefin comprises ethene and preferentially is propylene, being used for that hydrocarbon feed is converted into the thermal equilibrium of the known catalytic conversion process of light olefin (particularly propylene) can be more even, and the condition of composition that particularly can be by selecting whole raw materials and reactor is regulated the thermal equilibrium of particular reactor.
When having crystalline silicate catalyst of the present invention, one or more C 4Or more the higher alkene cracking becomes light olefin (C particularly 2And C 3Alkene, more preferably propylene) be thermo-negative reaction.Therefore in the olefin cracking technology of prior art, for example be disclosed in the technology of WO-A-99/29802, need careful control thermal equilibrium, to solve the endothermic nature of olefin cracking technology.On the contrary, use identical catalyzer, the C that uses in catalyzed conversion the inventive method 1To C 6Aliphatic series heterocompound (particularly methyl alcohol, it is converted into alkene and water) is thermopositive reaction.Therefore, because the present invention includes make the mixture that comprises first part and second section hydrocarbon feed by containing the reactor of this crystalline silicate catalyst, so that make the effluent that contains light olefin, so obtain thermal equilibrium between heat absorption that can take place at the same time and the thermopositive reaction, one or more C are contained in described first part 4Or high-grade alkene more, described second section contains at least a C that is selected from alcohol, ether, carbonyl compound and composition thereof 1To C 6The aliphatic series heterocompound.This provides operational advantage, particularly allows reactor easier operation under adiabatic condition.
Referring now to following non-limiting examples the present invention is described in more detail.
Embodiment 1
In embodiment 1, in laboratory scale fixed-bed reactor, place MFI-type crystalline silicate catalyst.This catalyzer comprises the silicon zeolite, and its silicon/al atomic ratio is 273 and by above-mentioned dealuminzation prepared.
More specifically, the silicon zeolite catalyst is by in the whirl test stove, prepares in 550 ℃ of following use steam decatize 4.2kg silicon zeolites 48 hours.Afterwards, the silicon zeolite of 2kg decatize is used the sodium-salt aqueous solution (EDTA-Na of ethylenediamine tetraacetic acid (EDTA) 2) handle, for 2kg silicon zeolite, need 8.4 liter of 0.055 molar solution.Handled 18 hours at boiling temperature.Filter the silicon zeolite then, thoroughly wash with deionized water.This technology is extracted aluminium from the silicon zeolite.
Afterwards, use kneader, the catalyzer that Guittard type M5 No.2295 kneader preparation is specifically extruded.Particularly, the silicon zeolite that 1640g is treated, 112g silica powder (Degussa FK500) and the 726g silicon sol (Nyacol 2040 of EKA, contain about 41 weight % silicas) mixed for several minutes with homogenizing they, in mixture, add 600ml distilled water then, obtain slurry, additionally mixed is 30 minutes then.After mixing 30 minutes, in mixture, add 10g polyelectrolyte solution (Nalco 9779), mediated 1 minute.Add 30g methyl hydroxyl ethyl cellulose (Tylose is from HoechstMHB1000P2) then.Loss on ignition (LOI) is about 33wt%.Forcing machine (Alexanderwerk type AGMRNo.04231162) is equipped with 2.5mm template mouth, and it is the quadralobe shape.Slurry passes through this forcing machine 2 to 3 times.Gained extrudate air-dry overnight, then in loft drier 110 ℃ dry 16 hours down, heating rate is 60 ℃/hour, then 600 ℃ temperature lower calcination 10 hours.Finally, catalyzer is carried out ion-exchange, use NH thus 4The catalyzer that twice ion-exchange 1740g of Cl (0.5 mole and 7310ml solution) extrudes, for the first time the time be 18 hours and for the second time the time be 3 hours, twice all is to carry out under the boiling temperature of solution.At last, filtering catalyst, washing and 400 ℃ of temperature lower calcinations 3 hours.
Gained modification silicon zeolite catalyst is the broken extrudate particle form of 35-45 sieve mesh.Surface-area is 339m 2/ g and pore volume are 1.1cm 3/ g.Loss on ignition is 1.7wt%.The chemical analysis demonstration of catalyzer consists of SiO 299.59wt%, Al 2O 30.31wt% and Fe 2O 30.06wt%.This provides silicon/al atomic ratio is 273.The silicon zeolite content is 80wt%.
The laboratory scale reactor comprises that diameter is that 11mm and length are the pipe of 500mm.Catalyzer 10ml (5.98g) is housed in this pipe.The top of reaction tubes and bottom all are filled with the ceramic inert particle of 1.6mm diameter.Place thermocouple well at inside reactor, to measure the temperature profile of catalyst bed.
In nitrogen, with 50 ℃/hour speed reactor heatings to reach 560 ℃ service temperature.Operant response device under atmospheric pressure.
Shown in table 1 (wherein MW represents molecular weight, and O represents alkene, and D represents diene, and P represents that paraffinic hydrocarbons and A represent aromatic substance), in reactor, add raw material.Compound material comprises the C that contains alkene 4+ fraction and the methyl alcohol fraction that contains the 30wt% methyl alcohol of having an appointment that mixes are based on the gross weight of compound material.The weight ratio of methyl alcohol and unsaturated hydrocarbons in the raw material (alkene and diene) is about 0.8:1.
The LHSV of raw material is 10h -1Contain in alkene part and the methyl alcohol-flow velocity of CH2 is 72g/h.Reactor inlet temperature is adjusted to 560 ℃.Top hole pressure is set in 1.5 crust (150kPa).Production time, (TOS) was less than 30 hours.Use the composition of chromatogram arrangement on-line analysis effluent, this device has the 40m microbore post from Agilent Technologies.Because the dependency between iso-butylene and the n-butene has the PoraplotU post and carries out the stratographic analysis second time in the little gas chromatograph (Micro G C) from Agilent Technologies.
After the selected production time, stop raw material and flow, use the nitrogen purging reactor tube, and be cooled to 300 ℃.Use the sequence of steps regenerated catalyst shown in the table 2 then.Burn all reactor coke under controlled temperature and controlled nitrogen and air velocity, the amount (0.6wt%) by restriction oxygen particularly is with the heat release of the oxidizing reaction of control carbon.Then, be used for next circulation with the nitrogen purging reactor.This regenerative process makes activity of such catalysts, selectivity and stability recover fully.
Fig. 1 illustrates for embodiment 1, ethylene yield (weight percent) and productivity of propylene (weight percent) and the relation between the production time (TOS).Olefins yield among Fig. 1 is based on alkene.
In order to consider that methanol conversion is the contribution of ethene and propylene among the embodiment 1, the productive rate of stdn ethene and propylene is with based on ＂ alkene+CH 2＂ supposes that each methanol molecules constitutes ＂ CH for any alkene that exists in the raw material 2The ＂ source.The productive rate of Fig. 2 display standardization is (with alkene+CH 2The meter) and the production time between relation.
Fig. 3 has shown propylene/ethylene productive rate ratio and the relation between the production time.
From Fig. 1, as can be seen, the propylene/ethylene productivity ratio is from about 3 in 2 and 3, increases to the value that was increased to up to about 25 hours greater than 5 along with the production time.
Should be noted that the methyl alcohol in the raw material transforms fully,, in effluent, also do not monitor out methyl alcohol or dme (DME) even at the circulation terminal point.Consider and use flame ionization detector in effluent, not monitor water that conversion is used to obtain the gas chromatograph results of the data of Fig. 1 to 3, obtains olefins yield.
Fig. 4 shows C in the effluent 2And C 3The composition of fraction and the relation between the production time.For C 2And C 3Fraction, respectively, C 2Show that ethene is for whole C 2Part by weight, and C 3Fraction shows that propylene is for whole C 3Weight ratio.
Embodiment 2
In embodiment 2, use identical raw material, rate of catalyst flow and LHSV, repeat the technology of embodiment 1, but 540 ℃ than the low reactor temperature under.Corresponding results is presented among Fig. 1 to 4.
Comparative Examples 1
In this Comparative Examples, use identical catalyzer to repeat embodiment 1 with different raw materials, this raw material does not contain methyl alcohol, and the hydrocarbon composition sees table 3.This raw material and the compound material that is used to prepare embodiment 1 and 2 to contain the alkene fraction identical, but do not comprise the interpolation methyl alcohol of 30wt%.The olefin(e) centent of raw material correspondingly is higher than the compound material that also contains the methyl alcohol part that is used for embodiment 1 and 2 and contains the alkene part.CH 2Flow velocity is 60g/h, and LHSV is identical with embodiment 1.Temperature of reactor is 560 ℃.Corresponding results sees Fig. 1 to 4.
Comparing embodiment 1 and 2 and the result of Fig. 1 to 4 of Comparative Examples 1 shows with what methyl alcohol replaced certain proportion (being 30wt% in an embodiment) to contain alkene hydrocarbon feed (containing the 50wt% alkene of having an appointment), can cause the increase slightly of productivity of propylene under identical temperature in.Yet Fig. 1 and 2 also illustrates, and methyl alcohol is joined to contain significantly reduced ethylene yield in the olefin feedstock, particularly after production is carried out about 10 hours.And, if temperature in reduces, be reduced to 540 ℃ from 560 ℃ in an embodiment, when methyl alcohol being joined when containing in the alkene part, ethene and productivity of propylene correspondingly reduce, but the productivity of propylene 540 ℃ under keep and higher temperature at 560 ℃ under contain alkene and not contain the productivity of propylene of hydrocarbon feed of methyl alcohol basic identical.
As can be seen from Figure 2, for based on ＂ alkene+CH 2The standardized productive rate of ＂, the relation between ethene and the productivity of propylene is identical to those shown in Fig. 1 basically.Comparing embodiment 1 and Comparative Examples 1 (all being to carry out under the same reactor temperature in), the existence of methyl alcohol has positive effect slightly for productivity of propylene, and has reduced ethylene yield.
No matter Fig. 3 shows reactor inlet temperature whether identical (embodiment 1) or lower (embodiment 2), the propylene/ethylene productivity ratio increases by methyl alcohol being joined contain in the alkene hydrocarbon feed.This is because owing to add the generation that methyl alcohol has reduced ethene.In addition, the propylene/ethylene ratio is tended to along with the production time increases gradually, and this is that the generation of ethene reduces gradually along with the increase of production time because join when containing in the alkene hydrocarbon feed when methyl alcohol.And, if reduce reactor inlet temperature, adding methyl alcohol simultaneously to containing in the alkene hydrocarbon feed, the propylene/ethylene productivity ratio is tended to increase.
In Fig. 4, in hydrocarbon feed, exist methyl alcohol to tend to strengthen as can be seen to alkene (C 2And C 3Fraction) selectivity.This means for C 3Cut, purified propylene increases, and for C 2Cut, ethene purity increases.
Thus generally speaking, embodiment and Comparative Examples have proved that olefinic logistics and methyl alcohol can be converted into light olefin simultaneously.Use the methyl alcohol that injects altogether to cause under identical reactor inlet temperature, increasing slightly productivity of propylene.More importantly, can obtain higher propylene/ethylene productivity ratio by injecting methyl alcohol altogether, and lightweight C 2And C 3Olefin(e) centent in the cut can significantly increase.
Fig. 5 is presented at the relation between the temperature and position in the reactor of Comparative Examples 1, wherein has a plurality of curves, and every curve all is begin (the last production time is about 115 hours) that obtain under the specific production time that finishes from conversion process.Curve moves between the Origin And Destination of production time as shown in Figure 5 gradually.Even in Comparative Examples 1, reactor with the adiabatic model operation, can not find out obviously that the hydrocarbon feed with 560 ℃ of importings enters into the top of catalyst bed, but the temperature at catalyst bed top sharply descends when the olefin cracking reaction takes place at the catalyst bed top.The size (amplitude) of the negative ＂ temperature peaks of ＂ is the darkest in the beginning of production time, reduces gradually during inactivation gradually at catalyzer.Yet along with the increase of production time, the minimum temperature value of every curve remains on same position substantially.This catalyzed conversion that has clearly illustrated alkene absorbs heat, and causes the thermal unbalance in the reactor.
On the contrary, Fig. 6 has shown the similarity relation of temperature and position in the reactor, but for embodiment 1, but wherein reactor inlet temperature comprises methyl alcohol and one or more C with 560 ℃ of identical hydrocarbon feeds of Comparative Examples 1 4Or high-grade alkene more.Similarly, along with the variation of production time shows many curves, from the origin-to-destination (about 29 hours) of production time.As can be seen from Figure 6, sharply increase in the head temperature of catalyst bed, this represents that methyl alcohol at first methanol of reaction conversion reaction is heat release when compound hydrocarbon feed enters into reactor, and this causes temperature to raise.Along with the increase of production time causes catalyzer inactivation gradually, thermal spike reduces, and from the top of catalyst bed at least in part to the end displacement of catalyst bed.
Comparison diagram 5 and 6, as can be seen for technology of the present invention, compare with the Comparative Examples of the thermo-negative reaction that the olefin catalytic conversion only takes place, for common production time greater than 10 hours, temperature distribution in the catalyst bed is more even, is illustrated in the thermal equilibrium that has higher degree between the heat release of competition and the thermo-negative reaction.
Table 1
Methyl alcohol (wt%) 30.03 paraffinic hydrocarbonss (wt%) 31.22 alkene (wt%) 36.54 diene (wt%) 0.69 aromatic substance (wt%) 1.53 average MW 50.4
Alkene rate (Olefinicity) (wt%)
O2+D2/(O2+D2+P2) -O3+D3/(O3+D3+P3) -O4+D4/(O4+D4+P4) 55.6O5+D5/(O5+D5+P5) 60.0O6+D6/(O6+D6+P6+A6) 48.4O7+D7/(O7+D7+P7+A7) 39.7O8+D8/(O8+D8+P8+A8) 43.5
Table 2
Temperature Nitrogen (NL/h) Air (NL/h)
310℃ 30 -
Oblique line rises, 50 ℃/h 31.5 0.9
500℃，6h 31.5 0.9
560℃ 31.5 0.9
560℃，10h 31.5 0.9
560℃ 30 -
Table 3
Figure C200480030670D00241

Claims (30)

1. the convert hydrocarbons raw material is to provide the method for the effluent that contains light olefin, this method comprises that the hydrocarbon feed that makes the mixture that contains first part and second section comprises the effluent of propylene through the reactor that contains crystalline silicate catalyst with preparation, and one or more C are contained in described first part 4Or high-grade alkene more, described second section contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof, described crystalline silicate be selected from following at least a: silicon/al atomic ratio is that the MFI-type crystalline silicate of 180-500 and silicon/al atomic ratio are 250 to 500 MEL-type crystalline silicate, and described MFI-type crystalline silicate and MEL-type crystalline silicate have experienced steaming step.
2. according at least a C that the process of claim 1 wherein in the second section 1To C 6The aliphatic series heterocompound and the first part of raw material and the weight ratio of the whole hydrocarbon in the second section are 15 to 85%.
3. according to the method for claim 2, at least a C in the second section wherein 1To C 6The aliphatic series heterocompound and the first part of raw material and the weight ratio of the whole hydrocarbon in the second section are 25 to 50%.
4. according to each method among the claim 1-3, the wherein at least a C in the second section 1To C 6The weight ratio of the whole unsaturated hydrocarbons in the first part of aliphatic series heterocompound and raw material is 0.5:1 to 2:1.
5. according to the method for claim 4, at least a C in the second section wherein 1To C 6The weight ratio of the whole unsaturated hydrocarbons in the first part of aliphatic series heterocompound and raw material is 0.75:1 to 1:1.
6. according to each method among the claim 1-5, wherein the second section of hydrocarbon feed contains following at least a: methyl alcohol, ethanol, dme, diethyl ether and composition thereof.
7. according to the method for claim 6, wherein the second section of hydrocarbon feed comprises methyl alcohol.
8. according to the method for claim 6 or 7, wherein reactor also is supplied with steam.
9. method according to Claim 8, wherein hydrocarbon feed contains the steam of 80wt% at the most.
10. according to each method among the claim 1-9, wherein hydrocarbon feed is through crystalline silicate at reactor inlet temperature under 460 to 580 ℃ the condition.
11. according to the method for claim 10, wherein hydrocarbon feed is through crystalline silicate at reactor inlet temperature under 540 to 560 ℃ the condition.
12., be 1 to 20h wherein at LHSV according to each method among the claim 1-11 -1Condition under, hydrocarbon feed is through crystalline silicate.
13. according to each method among the claim 1-12, wherein when through crystalline silicate, the dividing potential drop of at least a or multiple alkene in the raw material is 10 to 200kPa.
14. according to each method among the claim 1-13, wherein when the time through crystalline silicate, at least a C in the raw material 1To C 6The dividing potential drop of aliphatic series heterocompound is 10 to 400kPa.
15. according to each method among the claim 1-14, wherein crystalline silicate catalyst comprises that silicon/al atomic ratio is 250 to 500 silicon zeolite.
16. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises hydrotreated original C 4Raw material.
17. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises slight catalytic pyrolysis petroleum solvent.
18. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises raffinate 1 raw material or raffinate 2 raw materials.
19. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises raffinate 2 raw materials from methyl tertiary butyl ether or Ethyl Tertisry Butyl Ether device.
20. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises the raffinate from the olefin metathesis device.
21. according to the method for claim 20, wherein said raffinate from the olefin metathesis device is from being used for from the raffinate of the olefin metathesis device of ethene and butylene production propylene.
22. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises the logistics that contains hydrotreated alkene from the fluid catalytic cracking device.
23. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises the logistics that contains hydrotreated alkene from viscosity breaker.
24. according to each method among the claim 1-15, wherein the first part of hydrocarbon feed comprises the logistics that contains hydrotreated alkene from delay coking stove.
25. according to each method among the claim 1-24, wherein the first part of hydrocarbon feed comprises the product of methyl alcohol to olefin process, it contains C 4+ alkene.
26. according to each method among the claim 1-25, wherein effluent contains C 4The circulation of the fraction of+alkene is gone back through reactor, with at least a portion of the first part that constitutes hydrocarbon feed.
27. second charging be infused in the reactor purposes in the alkene in the catalytic cracking hydrocarbon charging on the MFI-type crystalline silicate catalyst comprises propylene with manufacturing the method for effluent altogether, it is used for making the thermal equilibrium of this reactor more even, it is 250 to 500 that this MFI-type crystalline silicate catalyst has silicon/al atomic ratio, and this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
28. second charging be infused in the reactor purposes in the alkene in the catalytic cracking hydrocarbon charging on the MFI-type crystalline silicate catalyst comprises propylene with manufacturing the method for effluent altogether, it is used for increasing effluent propylene/ethylene ratio, it is 250 to 500 that this MFI-type crystalline silicate catalyst has silicon/al atomic ratio, and this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
29. second charging be infused in the reactor purposes in the alkene in the catalytic cracking hydrocarbon charging on the MFI-type crystalline silicate catalyst comprises propylene with manufacturing the method for effluent altogether, it is used to increase the C from this effluent 3Propylene ratio in the cut, it is 250 to 500 that this MFI-type crystalline silicate catalyst has silicon/al atomic ratio, this second charging contains at least a C 1To C 6The aliphatic series heterocompound, described aliphatic heterocompound is selected from alcohol, ether, carbonyl compound and composition thereof.
30. each purposes among the claim 27-29, wherein second charging comprises methyl alcohol, and the hydrocarbon charging contains one or more C 4Or high-grade alkene more, the weight ratio of the whole unsaturated hydrocarbons in methyl alcohol in second charging and the hydrocarbon charging is 0.5:1 to 2:1, reactor inlet temperature is 540 to 560 ℃.
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